Electronic Supplementary Information
Extended lead(II) architectures engineered via tetrel bonding interactions
Ghodrat Mahmoudi,*a Ennio Zangrando,b Mariusz P. Mitoraj,*c Atash V. Gurbanov,d Fedor I.
Zubkov,e Maryam Moosavifar,a Irina A. Konyaeva,f,g Alexander M. Kirillov*h and Damir A. Safin*i
aDepartment of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran.
E-mail: [email protected]
bDepartment of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste,
Italy
cDepartment of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R.Ingardena 3, 30-060
Cracow, Poland. E-mail: [email protected]
dDepartment of Chemistry, Baku State University, Z. Khalilov Str. 23, AZ1148, Baku, Azerbaijan
e Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University),
6 Miklukho-Maklaya St., Moscow, 117198, Russian Federa
fLimited Liability Company «NIOST», Kuzovlevski trakt 2, 634067, Tomsk, Russian Federation
gDepartment of Technology of Organic Substances and Polymer Materials, National Research Tomsk Polytechnic
University, Lenin ave. 43, 634050 Tomsk, Russian Federation
hCentro de Química Estrutural, Complexo I, Instituto Superior Técnico,Universidade de Lisboa, Av. Rovisco Pais,
1049-001, Lisbon, Portugal. E-mail: [email protected]
iInstitute of Chemistry, University of Tyumen, Perekopskaya Str. 15a, 625003 Tyumen, Russian Federation. E-
mail: [email protected], [email protected]
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018
Fig. S1. 2D and decomposed 2D fingerprint plots of observed contacts for 3.
Fig. S2. (Top) Cluster model of 3 together with the fragmentation pattern applied in the ETS-NOCV analysis.
(Bottom) The overall deformation density Δρorb with the corresponding orbital interaction energies ΔEorb as well
as the QTAIM molecular graph demonstrating formation of NH-O, CH-O and CH-HC charge delocalizations.
Fig. S3. (Top) Molecular electrostatic potentials for NO3– and CH3COO– (DFT/ADF/BLYP-D3/TZP). (Bottom) The
ETS-NOCV results describing bonding between PbII and the corresponding anion.
Table S1. Selected bond lengths (Å) and angles (°) for 1 and 2
1 2
Pb–N2-Py 2.679(2) 2.732(6)
Pb–N3-Py 2.695(2) 2.894(7)
Pb–Nimine 2.602(2) 2.659(6)
Pb–OC=O 2.679(2) 2.499(5)
Pb–Onitrate/methoxide 2.504(2), 2.640(2), 2.778(2), 2.826(2) 2.187(5)
Pb∙∙∙Otetrel 3.117(2) —
Table S2. Selected bond lengths (Å) and angles (°) for 3 and 4
3 4
Pb(1) Pb(2)
Pb–N2-Py 2.492(10) 2.535(3) 2.563(4)
Pb–Nimine 2.563(11) 2.480(3) 2.700(4)
Pb–OC=O 2.619(7) 2.445(3) 2.599(3)
Pb–Onitrate/acetate 2.430(13), 2.655(11), 2.755(10) 2.338(3), 2.787(3) 2.552(3), 2.613(3), 2.626(3), 2.729(4), 2.916(3)
Pb∙∙∙Otetrel 3.061(11), 3.091(13), 3.275(13), 3.353(13) 2.995(3), 3.518(3) —
Pb∙∙∙Ntetrel — 3.143(4) —
Table S3. Classic hydrogen bond lengths (Å) and angles (°) for 1, 3 and 4
D–H∙∙∙A d(D–H) d(H∙∙∙A) d(D∙∙∙A) (DHA)
1a N(3)–H(3N)∙∙∙O(5) 0.82(3) 2.00(3) 2.787(3) 160(3)
3b N(3)–H(3N)∙∙∙O(5)#1 0.86 2.45 3.025(16) 124
N(3)–H(3N)∙∙∙O(6)#2 0.86 2.24 3.044(16) 155
4c N(4)–H(4N)∙∙∙O(7) 0.88 1.98 2.837(5) 165
aSymmetry transformations used to generate equivalent atoms: x, –1/2 – y, 1/2 + z.bSymmetry transformations used to generate equivalent atoms: #1: 1 – x, 1 – y, 1 – z; #2: –x, 1 – y, 1/2 + z.cSymmetry transformations used to generate equivalent atoms: 1 – x, 1/2 + y, 3/2 – z.
Table S4. π∙∙∙π interaction distances (Å) and angles (°) for 1 and 2a
Complex Cg(I) Cg(J) d[Cg(I)–Cg(J)] α β γ slippage
1b Cg(1) Cg(1)#1 3.5258(15) 0.00(13) 13.9 13.9 0.846
Cg(2) Cg(2)#2 3.7395(15) 0.02(12) 28.0 28.0 1.757
Cg(2) Cg(2)#3 3.6520(15) 0.02(12) 25.0 25.0 1.544
2c Cg(4) Cg(5)#1 3.707(5) 10.5(4) 19.8 26.3 1.256
Cg(4) Cg(5)#2 3.898(5) 10.5(4) 33.7 26.7 2.164
Cg(5) Cg(4)#3 3.898(5) 10.5(4) 26.7 33.7 1.754
Cg(5) Cg(4)#4 3.707(5) 10.5(4) 26.3 19.8 1.642
aCg(I)–Cg(J): distance between ring centroids; α: dihedral angle between planes Cg(I) and Cg(J); β: angle Cg(I) → Cg(J) vector and normal to plane I; γ: angle Cg(I) → Cg(J) vector and normal to plane J; slippage: distance between Cg(I) and perpendicular projection of Cg(J) on ring I.bSymmetry transformations used to generate equivalent atoms: #1 –x, –y, –z; #2 1 – x, –1 – y, 1 – z; #3 1 – x, –y, 1 – z. Cg(1): N(1)–C(8)–C(9)–C(10)–C(11)–C(12), Cg(2): N(4)–C(3)–C(2)–C(6)–C(5)–C(4).cSymmetry transformations used to generate equivalent atoms: #1 –1 + x, –1 + y, z; #2 x, –1 + y, z; #3 x, 1 + y, z; #4 1 + x, 1 + y, z. Cg(4): N(1)–C(8)–C(12)–C(11)–C(10)–C(9), Cg(5): N(4)–C(5)–C(6)–C(7)–C(8)–C(9).